ConspectusWhile spectacular successes have been achieved in homogeneous catalysis with the use of achiral diphosphine ligands featuring a wide natural bite angle, such as XantPhos, chiral diphosphines that can induce a large P-M-P bite angle in their transition metal complexes are conspicuously less explored in asymmetric catalysis, probably due to the challenges in the identification and efficient construction of a suitable chiral backbone. In the past decade, a highly efficient synthesis of chiral aromatic spiroketals and the corresponding diphosphine ligands (SKPs) has been developed in this group.Based on a one-pot catalytic tandem double asymmetric hydrogenation-spiroketalization ring-closure reaction sequence, these SKP ligands featuring an extraordinarily long P???P distance and a flexible backbone have been readily prepared in large scale. Remarkably versatile coordination modes have been found in the complexes of SKP with some catalysis-relevant transition metals, for example, Pd, Cu, Au, and Rh. Wheclass of readily accessible SKP ligands featuring a chiral aromatic spiroketal skeleton have demonstrated unique adaptable structures in a variety of transition metal complexes and provided outstanding performance in some difficult asymmetric transformations. The works delineated herein would be expected to stimulate further research efforts on the application of this type of chiral ligand and to provide useful clues in the design of new chiral diphosphine ligands with adaptable bite angles for transition metal catalyzed asymmetric reactions.The global use of &gt;3000 per- and polyfluoroalkyl substances (PFASs) has given rise to chemical regulatory action. However, limited information exists regarding current and historical emissions for the majority of PFASs under currently implemented regulations. This study employed suspect and nontarget screening to examine the temporal trends of legacy and unregulated PFASs in liver of the endangered beluga whale (Delphinapterus leucas) population from the St. Lawrence Estuary in Canada collected from 2000 to 2017. A suite of 54 PFASs were tentatively identified, and were grouped into nine structurally distinct classes. Single-hydrogenated perfluoro carboxylic acids (H-PFCAs), single-hydrogenated sulfonamides (H-Sulfonamides), as well as other select sulfonamides were detected for the first time in wildlife. Greater concentrations of the majority of PFASs were determined in newborns and juveniles than in adults, suggesting effective placental and lactational transfer of PFASs. Legacy per- and polyfluoroalkyl acids and perfluorooctane sulfonamide in beluga whale liver were found to significantly decrease in concentration between 2000 and 2017, while unregulated short-chain PFAS alternatives, H-PFCAs, and odd-chain FTCAs were found to increase over time. The implementation of suspect and nontarget screening revealed class-specific temporal trends of PFASs in SLE beluga whales, and supported continuous emissions of unregulated PFASs into the environment.ConspectusInterstellar clouds and the outer reaches of protostellar and protoplanetary systems are very cold environments where chemistry is limited to processes that have little or no reaction barrier (in the absence of external energy input). This account reviews what is known about cation-ice reactions, which are not currently incorporated in astrochemical network models. Quantum chemical cluster calculations using density functional theory have shown that barrierless reactions can occur when gas phase cations such as HCO+, OH+, CH3+, and C+ are deposited on an icy grain mantle with energies commensurate with other gas phase species. When cations react with molecules on ice surfaces, the pathways and products often differ significantly from gas phase chemistry due to the involvement of water and other molecules in the ice. https://www.selleckchem.com/products/borussertib.html The reactions studied to date have found pathways to abundant and important astromolecules such as methanol, formic acid, and carbon dioxide that are very favorable and may be more effic reaction network models of the formation and destruction of molecules in interstellar clouds and protoplanetary systems. Further studies will involve characterizing additional rcactions and more extensive treatment of the most important cation-ice reactions to better ascertain reaction branching outcomes.The synthesis and photophysical properties of the heteropolynuclear Pt-Ag complex having cyclometalated rollover bipyridine ligands (bpy*) and bridging pyrazolato ligands are reported. The Pt2Ag2 complex was synthesized by two step reactions from a Pt(II) complex precursor having the rollover bpy* ligand, [Pt(bpy*)(dmso)Cl], with 3,5-dimethylpyrazole (Me2pzH) and a subsequent replacement of NH protons in the Me2pzH moieties with the Ag(I) ion. The Pt2Ag2 complex exists as a mixture of U- and Z-shaped isomers in solution, whose structures were clearly determined by single-crystal X-ray structural analyses. NMR studies using the single crystals revealed rapid isomerization of the Pt2Ag2 complexes in solution, although the Pt2Ag2 structures were supported effectively by the multiple metal-metal interactions. Furthermore, the Pt2Ag2 framework can capture a Ag(I) ion during the U-Z isomerization to afford a Pt2Ag3 core with the formation of Pt → Ag dative bonds. The Pt2Ag3 complex showed further aggregation to form a dimer structure in the presence of coordinating solvent via the crystallization process. The formation of Pt → Ag dative bonds significantly changes the emission energy from the Pt2Ag2 complex, while the emission spectra of U- and Z-isomers of Pt2Ag2 complex almost coincide with each other and their emissive properties are very similar. The density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations revealed the effects of additional Ag(I) ion on the photophysical properties of the heteropolynuclear Pt-Ag complexes bearing the rollover bpy* ligands.We examined the ZnGeN2-GaN solid-solution system (Zn1-xGe1-xGa2xN2) in the unexplored compositional region of x less then 0.10 to reveal the transitional structural and optical properties caused by the introduction of Ga. Fairly stoichiometric fine powder specimens with compositions of x = 0.02 and 0.05 were prepared by the gas-reduction-nitridation method, and their partially ordered Pna21 structure was identified by solid-state 71Ga NMR spectroscopy and time-of-flight neutron powder diffraction. The Rietveld refinement results of the neutron diffraction data showed that the introduction of 2 atom % Ga readily retards the cation ordering in ZnGeN2, and this composition-induced transition to the wurtzite disordered phase proceeds mostly in the range of x less then 0.10. The synthesized samples showed gradual red shifts of the absorbance and photoluminescence excitation spectra with their x value, consistent with their degree of disorder, indicating that the narrowing of the band gap achieved in the current system results primarily from the disorder of the cation sublattice accompanied by octet-rule violation, as has been predicted theoretically.